EP0276190B1 - Verfahren und Vorrichtung zum elektrolytischen Absetzen eines kontinuierlichen Nickelfilms auf Draht - Google Patents

Verfahren und Vorrichtung zum elektrolytischen Absetzen eines kontinuierlichen Nickelfilms auf Draht Download PDF

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Publication number
EP0276190B1
EP0276190B1 EP88420002A EP88420002A EP0276190B1 EP 0276190 B1 EP0276190 B1 EP 0276190B1 EP 88420002 A EP88420002 A EP 88420002A EP 88420002 A EP88420002 A EP 88420002A EP 0276190 B1 EP0276190 B1 EP 0276190B1
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EP
European Patent Office
Prior art keywords
nickel
wire
bath
tank
plating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88420002A
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English (en)
French (fr)
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EP0276190A1 (de
Inventor
Jacques Léfèbre
Philippe Giménez
Gabriel Colombier
Armand Golay
Jean-Sylvestre Safrany
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rio Tinto France SAS
Original Assignee
Aluminium Pechiney SA
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Publication date
Application filed by Aluminium Pechiney SA filed Critical Aluminium Pechiney SA
Publication of EP0276190A1 publication Critical patent/EP0276190A1/de
Application granted granted Critical
Publication of EP0276190B1 publication Critical patent/EP0276190B1/de
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0607—Wires

Definitions

  • the invention relates to a method and a device for electrolytically depositing, on parade, a continuous film of nickel in the form of globules of adjustable size on metallic wire for electrical use.
  • French Patent No. 2,526,052 belonging to the applicant, teaches a process and a device for coating a long length of metal with a metal layer. It applies in particular to direct nickel plating, that is to say without the application of intermediate layers, electrical conductors of aluminum or one of its alloys, with a diameter between 1.5 and 3 mm and used for either industrial or domestic purposes.
  • the process consists in passing the wire, previously freed from lubrication residues, firstly through a liquid current socket which will be called hereinafter activation bath where, by passing a continuous or pulsed electric current, it charges positively and acquires, under the action of acidic and / or saline compounds contained in the bath, a so-called active surface which is perfectly suitable for subsequent coating; then, through a nickel-plating bath where, by passing the same current, it becomes negatively charged and gradually becomes covered with nickel until it forms a continuous film.
  • This process made it possible to obtain, on wires traveling at nearly 300 m / minute, a nickel film with a thickness of a few microns having in particular good adhesion and a weak and non-evolving contact resistance, properties which are essential for producing conductors. reliable electrical.
  • This adhesion was such that the wire could then be drawn to a diameter of 0.78 mm without there being any detachment or tearing of the nickel coating.
  • the aforementioned patent also teaches a compact device in which the activation and nickel-plating tanks each have a length close to 5 meters and are each equipped with a planar electrode extending parallel to the wire over its entire path in the bath.
  • the Applicant has found that it is necessary to reduce the current density in the upstream part of the nickel-plating bath in order to see a layer of nickel appear in the form of globules which adhere and cover the substrate better and which confer low contact resistance.
  • This improvement has been accentuated by replacing the profile of the current density inherent in the prior process, namely a decreasing curve from the entry to the exit of the bath, a profile in which a regular growth succeeds a slow decay and, in particular , by locating the maximum density at a point in the bath located between a third of the length from the inlet and the middle while reducing as much as possible the difference between this maximum density and the minimum density.
  • the means of the invention consist, on the other hand, in adjusting the acidity of the nickel-plating bath to a pH value of between 1 and 5 because within this range, the Applicant has found that the size of the nickel globules with the advantages mentioned above and this especially as the acidity increases. These results are particularly clear for pH values between 2.5 and 3.5.
  • This acidity can be increased, for example, by increasing the amount of sulfamic acid in the nickel plating bath which, as described in the aforementioned patent further contains nickel chloride and orthoboric acid while in the plating bath. 'activation, we find the same constituents described in said patent.
  • the method of the invention can be applied to any metallic wire such as copper wire for example.
  • any metallic wire such as copper wire for example.
  • it finds a particular interest in the nickel plating of aluminum wires or in one of its alloys for electrical use because it allows, because of its relatively low specific mass and the lightening which results therefrom, a substantial saving of energy. when it is substituted for copper for making cables intended to equip, for example, land or air transport vehicles.
  • This process is particularly suitable for nickel plating of small section strands (less than 1 mm) because it gives a very adherent coating which makes it suitable for making strands and cables which can be obtained by simultaneously nickel plating several strands placed in vertical tablecloth in the same bath.
  • the invention also relates to a device for applying the method described above.
  • This device comprises, as in the aforementioned patent, in the direction of travel of the wire, a first tank containing the activation bath, a rinsing compartment, a second tank containing the nickel-plating bath, the two tanks each being equipped with at least two pairs of planar electrodes, each pair being formed of electrodes placed on either side of the wire or wires and at least partially immersed in their respective bath, the pairs of the activation bath being connected to a source of negative current and those of the nickel bath being connected to a positive current source.
  • the electrodes of at least one of said pairs are removable, placed at an adjustable distance from at least one neighboring pair and from the wire and which is interposed between each of said electrodes and the wire at least one removable screen made of electrically insulating material.
  • the device according to the invention consists firstly of pairs of electrodes that can be moved either along the length of the tank to bring them closer or away from each other or leave free spaces in particular at one of the ends of the tanks, or according to the other dimension of the tank to bring them closer or less of the wire (s) to be coated.
  • the current density profile along the wire knowing that the absence of electrodes decreases this density and that the approximation of the electrodes of the wire increases it.
  • the profile defined above can be obtained either by leaving a free space in the upstream part of the nickel-plating tank and / or downstream of the activation tank, or by bringing the electrodes of the wire in the part opposite to the aforementioned part.
  • the specific means for moving the electrodes they can be produced from the knowledge of a person skilled in the art.
  • the device of the invention also consists of the presence of at least one removable screen between each of the electrodes of at least one pair and the wire.
  • These screens are made of an electrically insulating material and preferably have good resistance to the activation or nickel-plating bath. These screens are placed more or less far from the wire and at least partially mask the electrodes so that they interrupt or deflect the lines of current flowing in the baths and therefore make it possible to reduce the current density at precise locations in the bath.
  • these screens are placed in the upstream part of the tank and / or downstream of the activation tank.
  • screens provided with holes of variable diameter.
  • the number of holes is varied as a function of the position of the screen in the tank and, in particular, their number is increased in the direction of travel of the wire.
  • the device thus designed is suitable for the treatment of one or more wires by providing in the walls of the tanks located at the end of suitable openings located next to each other and equipped with seals.
  • a circulation of the latter by means of pumps.
  • the device is also notably completed by a rinsing compartment intended to eliminate by means of demineralized water the bath which may have been entrained out of the nickel-plating tank, the water which wets the wire then being evaporated in a drying compartment.
  • All the rinsing tanks and compartments are designed as modular elements, of length and section adaptable to the coating problem posed and easily associable with each other.
  • FIG. 1 represents a perspective view of a nickel-plating tank cut lengthwise along a vertical plane placed a little in front of the plant of median symmetry .
  • the electrodes and the screens are suspended in the bath by means not shown which allow them to be moved longitudinally and transversely in the tank.
  • the bath is driven in a circulation movement from bottom to top by means of a pump, not shown, supplied by the flow of overflows 10 and which discharges said bath into the distribution ramp 11.
  • the strands obtained were each covered with an average thickness of nickel of 1.5 ⁇ m in the form of globules with a diameter of 1.0 ⁇ m, a representation of which at 3000 magnification is shown in FIG. 2 and which can be compared in FIG. 3 corresponding to the prior art and which gave much larger globules (3 wm) and not forming a continuous layer.
  • nickel-plated wires were stranded and wired, then insulated with materials approved by the aeronautics industry.
  • the invention finds its application in the nickel plating of metallic wires in particular of aluminum, of any diameter and, in particular, less than 1 mm and allows obtaining by stranding and wiring of light and reliable electrical conductors which are particularly advantageous for equipping spacecraft. air or land transport where energy saving by reducing equipment is much appreciated.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemical Vapour Deposition (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Physical Vapour Deposition (AREA)
  • Non-Insulated Conductors (AREA)
  • Conductive Materials (AREA)

Claims (18)

1. Verfahren zum elektrolytischen Abscheiden einer zusammenhängenden Nickelschicht in Form von Kügelchen steuerbarer Größe im Durchlauf auf metallischem Draht für elektrische Verwendung, bei dem man den Draht nach Entfettung bei seinem Durchleiten durch ein Aktivierungsbad unter Spannung einer Stromdichte, die ihn positiv lädt, dann, nach Spülung, bei seinem Durchleiten durch ein saures Vernickelungsbad unter Spannung einer Stromdichte, die ihn negativ lädt, und schließlich einem Spülen und einem Trocknen aussetzt, dadurch gekennzeichnet, daß man zwecks Verringerung der Größe der Kügelchen die Stromdichte längs der Bahn des Drahtes moduliert, die Stromdichte im Stromaufteil des Vernickelungsbades und/ oder Stromabteil des Aktivierungsbades verringert und die Azidität des Vernickelungsbades auf einen pH-Wert im Bereich von 1 bis 5 reguliert.
2. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß man die Stromdichte in der Durchlaufrichtung des Drahtes langsam wachsen und dann abnehmen läßt.
3. Verfahren nach dem Anspruch 2, dadurch gekennzeichnet, daß man die Stromstärke derart wachsen läßt, um ein Maximum zwischen dem ersten Drittel und der Mitte des Bades zu haben.
4. Verfahren nach dem Anspruch 3, dadurch gekennzeichnet, daß man den Abstand zwischen der Maximaldichte und der Minimaldichte zwecks Verringerung der Größe der Kügelchen verkleinert.
5. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß man die Azidität des Vernickelungsbades zwecks Verringerung der Größe der abgeschiedenen Kügelchen steigert.
6. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß die Azidität einen Wert im Bereich von 2,5 bis 3,5 pH-Einheiten hat.
7. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß man Draht aus Aluminium oder aus einer seiner Legierungen für elektrische Verwendung vernickelt.
8. Verfahren nach dem Anspruch 7, dadurch gekennzeichnet, daß man Draht eines Durchmessers unter 1 mm vernickelt.
9. Verfahren nach dem Anspruch 8, dadurch gekennzeichnet, daß man Draht in Form eines vertikalen Bündels wenigstens zweier getrennter Adern vernickelt, die anschließend verseilt werden.
10. Vorrichtung zur Anwendung des Verfahrens nach dem Anspruch 1, die in der Durchlaufrichtung (5) des Drahtes (4) eine das Aktivierungsbad enthaltende erste Wanne, ein Spülabteil, eine das Vernickelungsbad enthaltende zweite Wanne (1) aufweist, wobei die beiden Wannen jeweils mit wenigstens zwei Paaren ebener Elektroden (7) ausgerüstet sind, jedes Paar aus zu beiden Seiten des oder der Drähte angeordneten und wenigstens teilweise in ihr zugehöriges Bad eingetauchten Elektroden gebildet ist, die Paare des Aktivierungsbades an eine negative Stromquelle angeschlossen und die des Vernickelungbades an eine positive Stromquelle angeschlossen sind, dadurch gekennzeichnet, daß die Elektroden wenigstens eines der Paare lösbar in einem bezüglich wenigstens eines benachbarten Paares und bezüglich des Drahtes regulierbaren Abstand angeordnet sind und daß man zwischen jeder dieser Elektroden und dem Draht wenigstens einen lösbaren Schirm (8) aus elektrisch isolierendem Material einfügt.
11. Vorrichtung nach dem Anspruch 10, dadurch gekennzeichnet, daß der Abstand bezüglich eines benachbarten Paares derart reguliert wird, um einen freien Raum im Stromaufteil der Vernickelungswanne und/oder im Stromabteil der Aktivierungswanne zu lassen.
12. Vorrichtung nach dem Anspruch 10, dadurch gekennzeichnet, daß der Abstand bezüglich des Drahtes derart reguliert wird, daß er im Stromaufteil der Vernickelungswanne und/oder im Stromabteil der Aktivierungswanne größer ist.
13. Vorrichtung nach dem Anspruch 10, dadurch gekennzeichnet, daß die Schirme im Stromaufteil der Vernickelungswanne und/oder im Stromabteil der Aktivierungswanne angeordnet werden.
14. Vorrichtung nach dem Anspruch 10, dadurch gekennzeichnet, daß wenigstens einer der Schirme mit Löchern (9) versehen ist.
15. Vorrichtung nach dem Anspruch 14, dadurch gekennzeichnet, daß die Zahl von Löchern je nach der Lage des Schirms in der Wanne variabel ist.
16. Vorrichtung nach dem Anspruch 15, dadurch gekennzeichnet, daß die Löcherzahl in der Durchlaufrichtung des Drahtes in der Vernickelungswanne und in der umgekehrten Richtung in der Aktivierungswanne wächst.
17. Vorrichtung nach dem Anspruch 10, dadurch gekennzeichnet, daß auf die Vernickelungswanne ein Spülabteil und ein Trocknungsabteil folgen.
18. Vorrichtung nach dem Anspruch 10, dadurch gekennzeichnet, daß die Wannen und Abteile in Form von Elementen des modularen Typs sind.
EP88420002A 1987-01-06 1988-01-04 Verfahren und Vorrichtung zum elektrolytischen Absetzen eines kontinuierlichen Nickelfilms auf Draht Expired - Lifetime EP0276190B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8700952A FR2609292B1 (fr) 1987-01-06 1987-01-06 Procede et dispositif pour deposer electrolytiquement au defile un film continu de nickel sur du fil metallique a usage electrique
FR8700952 1987-01-06

Publications (2)

Publication Number Publication Date
EP0276190A1 EP0276190A1 (de) 1988-07-27
EP0276190B1 true EP0276190B1 (de) 1990-09-19

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EP88420002A Expired - Lifetime EP0276190B1 (de) 1987-01-06 1988-01-04 Verfahren und Vorrichtung zum elektrolytischen Absetzen eines kontinuierlichen Nickelfilms auf Draht

Country Status (16)

Country Link
US (1) US4741811A (de)
EP (1) EP0276190B1 (de)
JP (1) JPS63213694A (de)
CN (1) CN1008823B (de)
AT (1) ATE56758T1 (de)
AU (1) AU589106B2 (de)
BR (1) BR8800017A (de)
CA (1) CA1309690C (de)
DE (1) DE3860610D1 (de)
DK (1) DK388A (de)
ES (1) ES2019995B3 (de)
FI (1) FI880021A (de)
FR (1) FR2609292B1 (de)
IS (1) IS1431B6 (de)
NO (1) NO880019L (de)
PT (1) PT86493B (de)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1001859A3 (nl) * 1988-10-06 1990-03-20 Bekaert Sa Nv Inrichting voor het continu electrolytisch behandelen van draadvormige voorwerpen.
JP2003533597A (ja) 2000-05-18 2003-11-11 コラス・アルミニウム・バルツプロドウクテ・ゲーエムベーハー アルミニウム製品の製造方法
US6796484B2 (en) 2001-02-02 2004-09-28 Corus Aluminum Walzprodukte Gmbh Nickel-plated brazing product having improved corrosion performance
CN1304643C (zh) 2001-04-20 2007-03-14 克里斯铝轧制品有限公司 镀覆和预处理铝件方法
US6572743B2 (en) * 2001-08-23 2003-06-03 3M Innovative Properties Company Electroplating assembly for metal plated optical fibers
US6815086B2 (en) 2001-11-21 2004-11-09 Dana Canada Corporation Methods for fluxless brazing
US6994919B2 (en) * 2002-01-31 2006-02-07 Corus Aluminium Walzprodukte Gmbh Brazing product and method of manufacturing a brazing product
US7294411B2 (en) * 2002-01-31 2007-11-13 Aleris Aluminum Koblenz Gmbh Brazing product and method of its manufacture
US7056597B2 (en) * 2002-12-13 2006-06-06 Corus Aluminium Walzprodukte Gmbh Brazing sheet product and method of its manufacture
US7078111B2 (en) * 2002-12-13 2006-07-18 Corus Aluminium Walzprodukte Gmbh Brazing sheet product and method of its manufacture
US20060157352A1 (en) * 2005-01-19 2006-07-20 Corus Aluminium Walzprodukte Gmbh Method of electroplating and pre-treating aluminium workpieces
US7650840B2 (en) * 2005-02-08 2010-01-26 Dyno Nobel Inc. Delay units and methods of making the same
US8794152B2 (en) 2010-03-09 2014-08-05 Dyno Nobel Inc. Sealer elements, detonators containing the same, and methods of making
CN102790199B (zh) * 2012-08-22 2015-08-05 陈伟洲 锂离子电池正极极耳及其制造方法
CN103820831B (zh) * 2014-02-13 2016-08-24 德清县佳伟线缆有限公司 一种金属线材的电镀处理设备
CN118173330B (zh) * 2024-05-14 2024-07-19 山东无棣海丰电缆有限公司 一种海洋电缆加工用防腐蚀处理装置

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4097342A (en) * 1975-05-16 1978-06-27 Alcan Research And Development Limited Electroplating aluminum stock
US4126522A (en) * 1976-08-09 1978-11-21 Telefonaktiebolaget L M Ericsson Method of preparing aluminum wire for electrical conductors
FR2526052B1 (fr) * 1982-04-29 1985-10-11 Pechiney Aluminium Procede et dispositif pour revetir une grande longueur de metal d'une couche metallique

Also Published As

Publication number Publication date
CA1309690C (fr) 1992-11-03
BR8800017A (pt) 1988-08-02
DK388D0 (da) 1988-01-04
FR2609292A1 (fr) 1988-07-08
NO880019L (no) 1988-07-07
NO880019D0 (no) 1988-01-05
CN1008823B (zh) 1990-07-18
DE3860610D1 (de) 1990-10-25
EP0276190A1 (de) 1988-07-27
PT86493A (pt) 1989-01-30
CN88100133A (zh) 1988-07-20
FI880021A0 (fi) 1988-01-05
AU589106B2 (en) 1989-09-28
ATE56758T1 (de) 1990-10-15
FI880021A (fi) 1988-07-07
US4741811A (en) 1988-05-03
IS3303A7 (is) 1988-07-07
FR2609292B1 (fr) 1989-03-24
ES2019995B3 (es) 1991-07-16
PT86493B (pt) 1993-08-31
JPH0317920B2 (de) 1991-03-11
AU1005988A (en) 1988-07-07
DK388A (da) 1988-07-07
IS1431B6 (is) 1990-07-16
JPS63213694A (ja) 1988-09-06

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